EP0877724A1 - Processus de production de dihalodifluoromethanes et de leurs homologues - Google Patents

Processus de production de dihalodifluoromethanes et de leurs homologues

Info

Publication number
EP0877724A1
EP0877724A1 EP97904142A EP97904142A EP0877724A1 EP 0877724 A1 EP0877724 A1 EP 0877724A1 EP 97904142 A EP97904142 A EP 97904142A EP 97904142 A EP97904142 A EP 97904142A EP 0877724 A1 EP0877724 A1 EP 0877724A1
Authority
EP
European Patent Office
Prior art keywords
iodine
metal
recited
hfpo
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97904142A
Other languages
German (de)
English (en)
Other versions
EP0877724B1 (fr
Inventor
Zhen-Yu Yang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0877724A1 publication Critical patent/EP0877724A1/fr
Application granted granted Critical
Publication of EP0877724B1 publication Critical patent/EP0877724B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms

Definitions

  • TITLE PROCESS FOR MAKING DIHALODIFLUOROMETHANES AND THEIR HOMOLOGUES FIELD OF THE INVENTION This invention pertains to a process for making dihalodifluoromethanes and their homologues by reacting fluorinated epoxides and dihalogen compounds in the presence of selected metal and metal-containing promoters at elevated reaction temperatures.
  • Dihaloperfluoroalkanes which may be represented by X(CF2) n Y, where n is 1 to 7, are useful for making functional fluoromonomers and other useful organofluoromaterials.
  • the diiodoperfluoroalkanes are also useful as chain transfer reagents for fluoroelastomers and in the free radical polymerization of fluorinated vinyl monomers. See for example U.S. Patent Nos. 4,243,770 and 4,361 ,678, which are inco ⁇ orated herein by reference.
  • CF2I 2 is a useful starting material for making organofluoromaterials and as a chain transfer agent for fluoroelastomers, but preparation methods have been shown to have low yields.
  • HFPO hexafluorocyclopropylene oxide
  • This invention pertains to a process for making , ⁇ -dihaloperfluoro- methanes and their homologues, comprising: reacting a fluorinated epoxide with a dihalogen in the presence of a metal or metal-containing promoter according to Equation I, wherein said promoter is selected from the group consisting of Ni, Cul, Ni/Cu, and Ni/Zn:
  • Rp represents a perfluoroalkyl or a perfluoroalkyl with one or more ether oxygen, chlorine, bromine, iodine, hydrogen, sulfonyl fluoride, nitrile, ester, acyl chloride or acyl fluoride substituent; wherein X and Y are each independently selected from the group consisting of I, Br, and Cl; wherein n is 2 to 6; and that said dihaloperfluoroalkanes are recovered with a yield of about 70 weight percent or greater.
  • CF2XY dihalodifluoro- methanes
  • fluorinated acyl fluorides from fluorinated epoxides and dihalogens.
  • Rp in Equation I represents a perfluoroalkyl or a perfluoroalkyl with one or more ether oxygen, chlorine, bromine, iodine, hydrogen, sulfonyl fluoride, nitrile, ester, acyl chloride or acyl fluoride substituents, and serves to define the fluorinated epoxides useful in this invention.
  • a metal or metal-containing promoter is comprised of a zero-valent metal (e.g., Ni, Cu) or combination of metals (i.e., Ni/Cu, Ni/Zn) or a metal halide (e.g., Cul), usually in the form of a powder or slurry.
  • a metal or metal containing promoter may be a metal or combination of metals, which form a process vessel (e.g., tube, tank, autoclave, reactor), so that the vessel's surface promotes the reaction.
  • a test reaction can be run in the presence of a coupon or in a vessel made of the material in question, which would require minimum experimentation.
  • An example of a typical vessel material which does not show promoting capabitility is stainless steel 316, which is comprising of only 10-14% Ni. See Metals Handbook, American Society of Metals, Metals Park, OH 44073, 1985, p. 15.3. This is consistent with the disclosure summarized in Inorg. Chem., 31(2), 1994, pp. 329-331 as cited above.
  • a vessel such as an autoclave is charged with the dihalogen and the fluorinated epoxide material, of which HFPO is preferred, and the mixture is heated for a period of time, generally 8 to 20 hours. If the vessel is not comprised of the catalytic material, then the catalyst is charged to the vessel, with the reactants before mixing and heating. The amount of catalyst added is the lowest effective amount, which has been found to be about 1.5 mole percent. Additional catalyst may be added up to about 20 mole percent to increase the yield to greater than the 50% yield obtained with the 3 mole percent addition. After the reaction is completed, the resulting mixture is then separated into its components, with the preferred separation method being distillation.
  • dihaloperfluoroalkane is meant a fully-fluorinated alkane which has two halogens, specifically chlorine, bromine and iodine, in place of two fluorines. These halogens are on the terminal ends of the perfluoroalkane. The halogens may be the same or different.
  • dihalogen is meant a compound represented by XY, where X and Y are each independently Cl, Br or I. Non- limiting examples include I 2 , Cl 2 , Br 2 and ICI.
  • fluorinated acyl fluoride is meant a compound of the general formula RCOF, wherein R represents fluorinated aliphatic groups or fluorinated aliphatic groups substituted with one or more moieties selected from the group consisting of ether oxygen, chlorine, bromine, iodine, hydrogen, sulfonyl fluoride, nitrile, ester, acyl fluoride and perfluorophenyl.
  • product mixture is meant the combination of the products of a reaction.
  • X I, Br or Cl:
  • Reactions may be carried out in either liquid or gas phase, and either neat (in the absence of solvent) or in solution in inert solvents (e.g., solvents which have no chemical activity on the other materials present).
  • solvents include, but are not limited to, chlorofluorocarbons (e.g., CFCi 13), hydrofluorocarbons, perfluoroethers, and perfluorobenzenes.
  • Reaction temperatures are generally about 150°C to about 300°C, preferably about 180°C to about 210°C.
  • Ratios given are those for peak areas by GC or molar ratios based on NMR data as designated in the specific Examples.
  • High Resolution Mass Spectrometry (HRMS) was done using a Micromass-7070H (VG Analytical, Manchester, UK).
  • GC-MS was also done using the Micromass-7070H .
  • Ni and Ni/Cu catalyst were used.
  • the Ni was prepared according to the following procedure: To a stirred solution of 133 g of NiCl 2 in 1500 mL of water was slowly added 65.0 g of Zn at room temperature. The resultant mixture was stirred for 15 hours. Solids were filtered and poured into 10% HCl and the resulting mixture was stirred for 30 minutes. After filtration, the solids were washed with water, acetone and dried in a vacuum at 60 C C to give 15.5 g Ni.
  • the Ni/Cu was prepared according to the following procedure:
  • a 1-L Hastelloy ® C autoclave was charged with 381 g of iodine and then evacuated at low temperature. After 266 g of HFPO was added, the resulting mixture was heated at 185°C for 10 hours. Subsequently, 184 g of gas was obtained which was mainly CF3COF determined by 19 F NMR. Then, 458 g of liquid was washed with aqueous Na 2 SO3 solution and brine, and distilled to give a 395 g mixture of CF 2 I 2 , ICF 2 CF 2 I and ICF 2 CF 2 CF 2 I in a ratio of 240: 1 :4.8 (GC area), bp 104-106°C.
  • Hastelloy ® C Autoclave A 1-L Hastelloy ® C autoclave was charged with 254 g of iodine and then evacuated at low temperature. After 500 g of HFPO was added, the resulting mixture was heated at 185 °C for 30 hours. Then, 350.6 g of gas was obtained which was mainly CF 3 COF determined by 19 F NMR.
  • a 0.4-L stainless steel shaker tube was charged with 127 g of iodine, 2.0 g of freshly made Ni powder and 3.0 g of Zn powder and then evacuated at low temperature. After 90 g of HFPO was added, the resulting mixture was heated at 185°C for 8 hours. An amount of 120.0 g of dark liquid was obtained which was distilled to give 78.4 g of a mixture of CF 2 I 2 , ICF 2 CF 2 I, ICF 2 CF 2 CF 2 I and I(CF 2 ) 4 I in a ratio of 16.1 : 1.0: 1.1 :0.2 (by GC area).
  • Hastelloy ® C Autoclave A 1-L Hastelloy ® C autoclave was charged with 254 g of iodine and 150 mL of CFC j ⁇ 3 , then evacuated at low temperature. After 175 g of HFPO was added, the resulting mixture was heated at 186°C for 10 hours.
  • HFPO Hexafluoropropylene Oxide
  • Hastelloy ® C Shaker Tube A 0.4-L Hastelloy ® C shaker tube was charged with 80 g of bromine and then evacuated at low temperature. After 90 g of HFPO was added, the resulting mixture was heated at 200 °C for 6 hours. Then, 91.3 g of liquid was obtained, which was washed with aqueous Na SO 3 solution and brine and distilled to give 71.3 g of CF 2 Br 2 , bp 23-25 °C. 19 F NMR: +6.5 (s).
  • Hastelloy ® C Shaker Tube A 0.4-L Hastelloy ® C shaker tube was charged with 62 g of iodine monobromide and then evacuated at low temperature. After 58 g of HFPO was added, the resulting mixture was heated at 185°C for 6 hours.
  • HFPO Hexafluoropropylene Oxide

Abstract

On fait réagir des époxydes fortement fluorés avec des dihalogènes en présence de promoteurs de réaction métalliques ou contenant du métal afin d'obtenir des dihalofluorométhanes et leurs homologues. Les dihalodifluorométhanes obtenus sont utiles pour produire des monomères fluorés fonctionnels ainsi que d'autres substances organiques fluorées. Les diiodoperfluoroalcanes peuvent également être utiles en tant que réactifs de migration de chaîne pour les fluoroélastomères.
EP97904142A 1996-02-23 1997-02-06 Processus de production de dihalodifluoromethanes et de leurs homologues Expired - Lifetime EP0877724B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1216096P 1996-02-23 1996-02-23
US12160P 1996-02-23
PCT/US1997/001584 WO1997030957A1 (fr) 1996-02-23 1997-02-06 Processus de production de dihalodifluoromethanes et de leurs homologues

Publications (2)

Publication Number Publication Date
EP0877724A1 true EP0877724A1 (fr) 1998-11-18
EP0877724B1 EP0877724B1 (fr) 2001-06-13

Family

ID=21753663

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97904142A Expired - Lifetime EP0877724B1 (fr) 1996-02-23 1997-02-06 Processus de production de dihalodifluoromethanes et de leurs homologues

Country Status (5)

Country Link
US (1) US6002055A (fr)
EP (1) EP0877724B1 (fr)
JP (1) JP2000505082A (fr)
DE (1) DE69705202T2 (fr)
WO (1) WO1997030957A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0912474B1 (fr) * 1996-05-22 2003-01-02 E.I. Du Pont De Nemours And Company Procede utilisant du cf2i2 et des olefines pour produire des composes diiodofluores et ses produits
KR100704527B1 (ko) * 1999-08-31 2007-04-10 아사히 가라스 가부시키가이샤 Ｖｉｃ-디클로로산 플루오라이드의 제조 방법
JP4967297B2 (ja) * 2004-10-26 2012-07-04 旭硝子株式会社 新規エステル及びその製造方法
US7456314B2 (en) * 2006-12-21 2008-11-25 E.I. Du Pont De Nemours And Company Partially fluorinated ionic compounds
ITMI20071384A1 (it) * 2007-07-11 2009-01-12 Milano Politecnico Procedimento per la purificazione di composti alfa,omega-diiodioperfluorurati.
US10093761B2 (en) 2010-12-17 2018-10-09 3M Innovative Properties Company Fluorine-containing polymer comprising a sulfinate-containing molecule
CN104080854B (zh) 2011-12-16 2016-12-07 3M创新有限公司 来源于含亚磺酸根的分子的加工助剂组合物
PL2909162T3 (pl) 2012-10-17 2017-03-31 3M Innovative Properties Company Sposób wytwarzania alfa, omega-dijodo perfluoroalkanów
JP6820859B2 (ja) * 2015-02-27 2021-01-27 ザ ケマーズ カンパニー エフシー リミテッド ライアビリティ カンパニー ジヨードペルフルオロ−ｃ３〜ｃ７−アルカンの段階的合成
WO2016138247A1 (fr) * 2015-02-27 2016-09-01 The Chemours Company Fc, Llc Synthèse de diiodoperfluoro-c3 à c7-alcanes
CN107983343B (zh) * 2017-11-24 2020-12-11 上海化工研究院有限公司 一种脱羰氯化催化剂及其制备方法与应用
JPWO2022244481A1 (fr) * 2021-05-20 2022-11-24

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53125491A (en) * 1977-04-08 1978-11-01 Daikin Ind Ltd Fluorine-containing polymer easily curable and its curable composition
JPS5657811A (en) * 1979-10-17 1981-05-20 Daikin Ind Ltd Preparation of liquid fluorine-containing polymer
RU1297411C (ru) * 1984-12-25 1993-11-30 Предприятие П/Я А-7372 Способ получени дифтордибромметана

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9730957A1 *

Also Published As

Publication number Publication date
DE69705202T2 (de) 2001-11-22
JP2000505082A (ja) 2000-04-25
DE69705202D1 (de) 2001-07-19
EP0877724B1 (fr) 2001-06-13
US6002055A (en) 1999-12-14
WO1997030957A1 (fr) 1997-08-28

Similar Documents

Publication Publication Date Title
EP0877724B1 (fr) Processus de production de dihalodifluoromethanes et de leurs homologues
WO2004060849A1 (fr) Reaction selective d'oxyde d'hexafluoropropylene avec des fluorures de perfluoroacyle
AU622295B2 (en) Manufacture of 1,1,1,2-tetrafluoroethane
US6284933B1 (en) TFPX synthesis
JP2532885B2 (ja) ハイポフルオライト及びビス―ハイポフルオライト、並びにその製造方法
EP1175380B1 (fr) Preparation de fluoroolefines selectionnees
US6703533B1 (en) Preparation of selected fluoroolefins
JP4526826B2 (ja) フルオロハロゲンエーテルの製造方法
EP0151885B1 (fr) Procédé et intermédiaires pour un monomère vinylique fluoré
US6191314B1 (en) Process for obtaining (per)fluoropolyethers substituted at one or at both end groups with a halogen atom
JPH0552295B2 (fr)
EP0270956A1 (fr) Procédé de synthèse de perfluoroalcadiènes
EP0748318B1 (fr) Procede de preparation de polyfluorooxetanes
JP2506999B2 (ja) クロロトリフルオロエチレン及びトリフルオロトリクロロエタンからテロマ―を調製する方法
JP2729838B2 (ja) パーフルオロ（ビニルエーテル）類の低重合法
GB2056445A (en) Iodoacyl fluorides
JPH04139145A (ja) パーフルオロ（２―低級アルコキシプロピオン酸）フロリドの製造法
US4937391A (en) Process for preparing perfluoro-(2-bromoethyl-vinyl-ether)
CA1231727A (fr) Couplage de telomeres de chlorotrifluoroethylene
CA1236489A (fr) Fluoration de telomeres chlorofluores
EP0504285B1 (fr) Composes de fluorocarbones et leurs procedes de preparation
JP2877166B2 (ja) パーフルオロ（２―プロポキシプロピオン酸）フロリドの製造法
JPH0222740B2 (fr)
JPS6112896B2 (fr)
EP0614873A1 (fr) Oxydes de hexafluoropropylène et procédé pour leur préparation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19980819

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

17Q First examination report despatched

Effective date: 19990615

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

REF Corresponds to:

Ref document number: 69705202

Country of ref document: DE

Date of ref document: 20010719

ITF It: translation for a ep patent filed

Owner name: MARIETTI E GISLON S.R.L.

ET Fr: translation filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020206

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020903

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021031

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050206